Color photographic material

ABSTRACT

CYAN-FORMING COUPLER OF THE FOLLOWING FORMULA   1-HO,2-(A-N(-B)-SO2-(1,4-PHENYLENE)-O-R-NH-CO-),4-X-   NAPHTHALENE   WHEREIN X IS HYDROGEN, HALOGEN OR SULFO, R IS A HYDROCARBON CHAIN, AND A AND B ARE HYDROGEN, ALKYL, CYCLOALKYL, ARALKYL OR ARYL OR TOGETHER COMPLETE A TETEROCYCLIC RING, YIELD ON COLOR-FORMING DEVELOPMENT CYAN DYES WITH HIGH TRANSMISSION FOR BLUE LIGHT AND HIGH STABILITY TO MOIST HEAT. THE COUPLERS CAN BE USED IN COMBINATION WITH RED MASKING COUPLERS.

United States Patent Oflice 3,684,515 Patented Aug. 15, 1972 3,684,515 COLOR PHOTOGRAPHIC' MATERIAL Walter Schulte, Oplad'en, Immo Boie, Cologne, Helmut Mader, Odenthal-Hahnenberg, and Rigobert Otto,

Leverkusen, Germany, assignors to Agfa-Gevaert Aktiengesellschaft, Leverkusen, Germany No Drawing. Filed Aug. 26, 1970, Ser. No. 67,255

Claims priority, appplication Germany, Sept. 2, 1969,

P 19 44 440.7 Int. Cl. G03c N40 US. Cl. 96-100 3 Claims ABSTRACT OF THE DISCLOSURE Cyan-forming coupler of the following formula wherein X is hydrogen, halogen or sulfo,

R is a hydrocarbon chain, and

A and B are hydrogen, alkyl, cycloalkyl, aralkyl or aryl or together complete a teterocyclic ring,

yield on color-forming development cyan dyes with high transmission for blue light and high stability to moist heat. The couplers can be used in combination with red masking couplers.

The invention relates to a color photographic material which contains new cyan-forming couplers and which is improved both in its color reproduction and stability.

In color photographic materials which are processed by chromogenic development to produce color photographs, it is known to build up the cyan part of the image from color-forming couplers which generally consist of derivatives of phenols or naphthols. Although numerous of such cyan-forming couplers are known, there is no cyan-forming coupler which ideally fulfils the many requirements necessary in photographic practice. In fact, most color-forming couplers have serious disadvantages. Thus, insuflicient stability of the residual coupler which has not been coupled with the color-forming developer to produce the dye image often causes discoloration of the image whites. The image dyes produced by coupling with oxidized color-forming developer frequently do not have the required absorption maximum and furthermore may manifest undesirably high side absorptions. Many dyes separate out in the form of comparatively coarse color grains, whereas in other cases the coupling reaction is too slow. Quite generally, the cyan dyes which are obtainable by chromogenic development "tend to have insuflicient stability to light, unsatisfactory resistance to hydrolysis and have an inconveniently high sensitivity to reducing agents.

Furthermore, many cyan-forming couplers have little or no kinetic compatibility with azo red masking couplers and, therefore, cannot be used in color corrected, or socalled masked, materials.

It is, therefore, an object of this invention to find cyanforming couplers which can be developed chromogenically to yield dyes which have improved absorption properties and increased stability and which do not themselves tend to yellow.

It has now been found that l-hydroxy-Z-naphthamides of the following general formula are particularly suitable for use as cyan-forming couplers in photographic silver halide emulsion layers:

In the above formula:

X=a hydrogen atom or a halogen atom such as a fluorine, chlorine or bromine atom, or is a sulphonic acid group;

R=a saturated, linear or branched bivalent hydrocarbon chain containing up to 18 carbon atoms, preferably 2 to 6 carbon atoms;

A=a hydrogen atom, or a linear or branched alkyl group containing up to 20 carbon atoms, a cycloalkyl group, such as cyclohexyl, an aralkyl group such as benzyl or phenylethyl, or an aryl group such as phenyl; and

B=a linear or branched alkyl group containing up to 20 carbon atoms, a cycloalkyl group such as cyclohexal, an aralkyl group such as benzyl or phenylethyl, or an aryl group such as phenyl; or

A and B together with the nitrogen. represent a 5-, 6- or 7- membered heterocyclic ring which may contain a further hetero atom such as piperidine, pyrrolidine, hexamethylene imine or morpholine.

The following are examples of suitable couplers:

M.P. C.)

I 1 0H -107 i I? C-NH-(CH2)2O-S O2-N\ Cu s'I C-NH(CHa)lO-S 02-N C1t a1 The synthesis of the cyan-forming couplers according to the invention is explained with the aid of the following reaction scheme:

A lHN The synthesis of coupler U is described in detail below.

Preparation of coupler US (a) N-[4-(p-chlorosulfophenoxy)-butyl]-phthalimide. 375 g. of chlorosulfonic acid are added at 2. C. to a solution of 245 g. of N-(4-phenoxylbutyl)-phthalimide in 1.8 litres of absolute chloroform. The mixture is then stirred without cooling for minutes and heated at 50 C. for one hour. After the addition of.600 g. of sodium chloride, the reaction mixture is poured onto 400 g. of anhydrous sodium carbonate and filtered under suction, and the solution is evaporated to dryness. The residue is recrystallized from benzene. M.P. 130 C.; yield 120 g.

(b) N-[4 (p-N'-methy1N'-n-octadecylsulfamyl-phenoxy)-butyl]-phthalimide.-l3.4 g. of methyl-n-octadecylamine are dissolved in 200 m1. of hot anhydrous tetrahydrofuran and 7 ml. of triethylamine, and 22 g. of N-[4- (p-chlorosulfophenoxy)-butyl] -phthalimide are added. After one hours boiling, the reaction product is precipitated with a mixture of ice and hydrochloric acid, removed by suction filtration, washed with water and recrystallized from propanol. M.P. l07-108 C.; yield g.

(c) 4-(p-N-methy1-N'-n-octadecylsulfamylphenoxy)-1- butylamine.--2O g. of methyl-n-octadecylamine are boiled for one hour with 150 m1. of ethanol and 2 g. of hydrazine, acidified with HCl, and boiled under reflux for /2 hour. The reaction mixture is then stirred into a mixture of sodium carbonate solution and ice, filtered under suction and washed with water, and the residue is recrystallized from propanol. M.P. 90 to 95 C.; yield 15 g.

(d) l hydroxy N-[4 (p-N-methyl-N'-noctadecy1- sulfamylphenoxy)-butyl] Z-naphthamide. Coupler I/5.- 15 g. of methyl-n-octadecylamine and 9 g. of phenyl 1- hydroxy-Z-naphthoate are heated to 160 C. and 0.1 mm. Hg for one hour. When cold, the residue is recrystallized from propanol. M.P. 76 C.; yield 12 g.

The cyan dyes obtained from the new color-forming couplers by chromogenic development have advantageous spectral properties. Their absorption curves have steep flanks and only a slight yellow side density. High permeability to blue light is therefore obtained. The new cyan dyes have greater stability to moist heat and light than cyan dyes obtained from known color-forming couplers of similar structure. The tendency of colorforming couplers which have not been coupled to discolor the layer is slight. Another advantage is that the new colorforming couplers if they are water-insoluble have low melting points and are highly soluble in organic solvents such as ethyl acetate or methylene chloride. They can, therefore, be easily emulsified in gelatin. The use of oilforming agents is therefore unnecessary. A specialadvantage of the new cyan-forming couplers is their good kinetic compatibility with certain azo red masking couplers, e.g. those described in German patent application P 19 44 441.8 which correspond to the following general formula:

F=a long chain alkyl group containing 10 to 20 carbon atoms or the group The following are examples of compounds which are eminently suitable for use together with the cyan-forming couplers according to the invention:

CODE 00011 III/4 on @oo-nn-mum HINO SOgNHs ,7 a OH I GO-NHQ isHn EH, N ii i HgNOISOAOzNH,

(fiM N I it o o omo-b -OOH| The cyan-forming couplers according to the invention and the red azo masks for use together with them according to the invention may be incorporated with the silver halide emulsion by one of the known methods. If, for example, the compounds are hydrophobic, they are incorporated in known manner by dissolving them in suitable organic solvents, e.g. in esters of aliphatic carboxylic acids, in par ticular in ethyl acetate, and emulsifying this solution with the silver halide emulsion which is ready for casting. This method may advantageously be modified by simultaneously using oily coupler solvents. This process has been disclosed in U.S. patent specification Nos. 2,304,940 and 2,322,027. If the couplers or masking couplers are alkali-soluble compounds, they may be added to the light sensitive silver halide emulsions in aqueous alkaline solution. The couplers and masking couplers may, of course, be added one after the other to the silver halide emul- 'sion or simultaneously from a common solution. The method by which they are added to the emulsion is not critical and the most suitable process can be easily cletermined by simple tests. Suitable light sensitive emulsions are emulsions of silver halides such as silver chloride, silver bromide or mixtures thereof, if desired with a small silver iodide content of up to 10 mols percent in one of the usual hydrophilic binders such as protein, in particular gelatine, polyvinyl alcohol, polyvinyl pyrrolidone, cellulose derivatives such as carboxyalkyl cellulose, especially carboxymethyl cellulose, or derivatives of alginic acid.

The emulsions may also contain the usual additives, e.g. spectral or chemical sensitizers, stabilizers, hardeners, plasticizers and the like.

Any color-forming developers which contain a primary amino group may be used for development. It is particularly advantageous to use those of the p-phenylene diamine type, e.g. N,N-dimethyl-p-phenylene diamine, N,N- diethyl-p-phenylene diamine, 2-amino-S-diethyl-amiuotoluene, N butyl-n-w-sulfo'butyl-p-phenylene diamine or 2- amino 5 (N ethyl-N-p-methanesulfonamidoethylamino)toluene.

EXAMPLE .1

Coupler I/ 1 is dissolved in 25 ml. of ethyl acetate and, after the addition of g. of dibutyl phthalate, emulsified in 200 ml. of 5% gelatin solution (containing 1.6 g. of the sodium salt of dodecylbenzene sulfonic acid) at 60 C. The emulsion is then mixed with 850 g. of 7.5% gelatin solution which contains 19.25 g. of silver bromide in dispersed form, and, after dilution with water to obtain the required viscosity for casting, the emulsion is poured on a transparent layer support. After drying, the film is exposed behind a grey Wedge and developed in a color-developer which contains Z-amino-S-diethylaminotoluene as color-developing substance. After bleaching and fixing, a cyan color wedge is obtained. The absorption maximum of this wedge was determined and its stability in light and moisture was tested under the following conditions:

(a) 1 day in a tropical cupboard (60 C., 95 to 100% relative humidity), (b) 1 day in hot vacuum (90 0,2 to 3 mm. Hg), (c) 30 days exposure to a fluorescent lamp.

The percentage reduction in color density measured at densities of 0.5 and 1.5 is shown in the following table:

20 g. of coupler I/1 are dissolved in 60 ml. of ethyl acetate and emulsified in known manner in 320 ml. of 10% gelatin. The emulsion contains 11 ml. of 10% aqueous saponin solution.

350 ml. of this emulsion are added with stirring to 1 kg. of a photographic silver bromide emulsion which contains 95 g. of gelatin and 0.4 mol of silver.

In addition, 150 ml. of a 5% aqueous alkaline solution of the azo masking coupler II/2 are added.

To this emulsion containing coupler and masking coupler are added 25 ml. of a 1% methanolic solution of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene, 30 ml. of a 10% aqueous saponin solution and 15 m1. of 0.5% aqueous chromium acetate solution, and the emulsion is poured out onto a layer support of cellulose triacetate in a thickness of about 4.5;! The pH of the layer is about 6.5 to 7.

After drying, the material is exposed through a stepless grey wedge and developed for 15 minutes in a developer of the following composition:

5 g. of 2-amino-5-(N-ethyl-N-B-methanesulfonamidoethylamino)-toluene sesquisulfate monohydrate, 5 ml. of benzyl alcohol,

1 0 2.5 g. of sodium hexametaphosphate, 1.85 g. of anhydrous sodium sulfite, 1.4 g. of sodium bromide, 0.5 mg. of potassium iodide, 12.5 g. of sodium hydroxide g. Of NflgBQOq' Water up to 1 litre.

Subsequent processing includes the following baths: Short stop bath 17 ml. of glacial acetic acid, 2.95 g. of anhydrous sodium acetate, Water up to 1 litre.

Hardening bath 0.3 g. of sodium hydroxide, 0.5 g. of sodium hexametaphosphate, 9.04 g. of sodium carbonate, 20 ml. of 37% Formalin, Water up to 1 litre.

Bleaching bath 6 g. of sodium hexametaphosphate, 42.0 g. of potassium ferricyanide, 12.0 g. of potassium bromide, 6.0 g. of disodium phosphate, 16.0 g. of monopotassium phosphate, Water up to 1 litre.

Fixing bath g. of ammonium thiosulfate, 10 g. of sodium sulfite, Water up to 1 litre.

Final bath 0.3 g. of sodium tetrapropylene benzene sulfonate, Water up to 1000 ml.

The processing times after development are as follows:

Short stop bath: 4minutes Hardening bath: 4 minutes Washing: 5 minutes Bleaching bath: 6 minutes Washington: 5 minutes Fixing bath: 8 minutes Washington: 10 minutes Final bath: 30 minutes.

A cyan dye is formed in the exposed areas, and the orange-red masking dye is preserved in the unexposed areas. Sensitometric determination shows that excellent masking of the material is obtained in the blue and green ranges of measurement.

EXAMPLE 3 A photographic emulsion is prepared as in Example 2 but instead of 350 m1. of emulsified coupler I/l it contains 370 ml. of emulsified coupler 31/2 and ml. of a 5% solution of the masking coupler II/4.

After processing, which is carried out as described in Example 2, a cyan wedge is again obtained in which there is excellent masking of the yellow and magenta side densities.

What is claimed is:

1. A light sensitive color photographic material comprising at least one silver halide emulsion layer and containing a cyan-forming coupler of the following general formula:

11 12 in which: R R R and R which which are the same or difler- X=a hydrogen or halogen atom or a sulfonic acid ent, are hydrogen atoms or alkyl groups, but at least group, one of the radicals represent an alkyl group contain- R=a saturated bivalent hydrocarbon chain containing ing to 20 carbon atoms,

up to 6 carbon atoms, 5 R OH, an alkoxy group or an amino group. A=hydrogen atom, or a linear or branched alkyl group 3. A color photographic "material according to claim 2, containing up to 20 carbon atoms, a cycloalkyl group, which contains a cyan-forming coupler of the formula: an aralkyl group or an aryl group, and 0H B=a linear or branched alkyl group containing up to 0 CH; 20 carbon atoms, a cycloalkyl group, an aralkyl 1U gqsmqcmhfloflws group or an aryl group. ONE

2. A color photographic material according to claim 1, which contains in addition an azo red masking coupler I r k of the following gfillelal formula: and which contains in addition a red masking coupler of 0H the formula:

N is a1 z, j Z: p

' N o 000 in which: 7 a a Na F=a long chain alkyl group containing 10 to 20 carbon References it the gmup Y UNITED STATES PATENTS 2,628,901 2/1953 Duerr 96--84 2,688,539 9/1954 'Heimbach et a1. 969 N 2,698,794 1/1955 Godowsky 9697 \R 3,556,796 1/1971 Eynde et al 961OO R; J. TRAVIS BROWN, Primary Examiner 40 .1 r us. 01. X.R.

96-9, Z and Z =the same or diiferent groups COR or 73135 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. ,.,.3,1 ,5 5 Dated August 5, 972

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Eolumn 9, line &9 of the Table, under the heading "Heating Vacuum I the number 5 should read 5 ColumnvlO, line &5, should. read Final bath: 30 seconds Signed and sealed this 6th day of February 1973.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSGHALK Attesting Officer Commissioner of Patents 

